C hyperfine interactions in the ground state of the negatively charged nitrogen vacancy ͑NV − ͒ center have been investigated using electron-paramagnetic-resonance spectroscopy. The previously published parameters for the 14 N hyperfine interaction do not produce a satisfactory fit to the experimental NV − electron-paramagnetic-resonance data. The small anisotropic component of the NV − hyperfine interaction can be explained from dipolar interaction between the nitrogen nucleus and the unpaired-electron probability density localized on the three carbon atoms neighboring the vacancy. Optical spin polarization of the NV − ground state was used to enhance the electron-paramagnetic-resonance sensitivity enabling detailed study of the hyperfine interaction with 13 C neighbors. The data confirmed the identification of three equivalent carbon nearest neighbors but indicated the next largest 13 C interaction is with six, rather than as previously assumed three, equivalent neighboring carbon atoms.

Electron paramagnetic resonance (EPR) and optical spectroscopy have been used to determine the structure and electronic state of nickel-nitrogen centres in natural diamonds and in synthetic diamonds enriched in 13C. The latter were grown in an Fe-Ni-C solvent/catalyst system at 1750 K, under stabilizing pressure, by the temperature gradient method and afterwards treated at high temperature and pressure. The parameters and directions of the 13C hyperfine structure (HFS) tensors for the NE1 centre were found to confirm the previously proposed model for this defect, with a nickel ion at the centre of a double semivacancy as the basic structural unit. In this unit the nickel atom has six atoms in its coordination shell. The NE1 centre has C2h symmetry, and the two equivalent nitrogen atoms in the coordination shell lie in the symmetry plane. New data on the HFS of 14N and 13C for the NE5 centre, also with C2h symmetry, indicated the same structural unit, but the two equivalent nitrogen atoms (and two equivalent carbon atoms) lie out of the symmetry plane and are related to one another by reflection in it. A new paramagnetic centre was found, labelled NE8, also with C2h symmetry, with four equivalent nitrogen atoms in the coordination shell all lying out of the symmetry plane. This centre is responsible for the 793.6 nm vibronic system in absorption and luminescence spectra. The new data have allowed a reinterpretation of the HFS tensors for the NE2 centre, which has C1 symmetry, suggesting that it has the same structure as NE1 but with one additional nitrogen atom in the coordination shell. The electronic states of these nickel-containing centres are discussed using the approach of Ludwig and Woodbury to transition metal ions in covalent crystals.

We report the identification of the nitrogen-vacancy-hydrogen complex in a freestanding nitrogen-doped isotopically engineered single crystal diamond synthesized by chemical vapor deposition. The hydrogen atom is located in the vacancy of a nearest-neighbor nitrogen-vacancy defect and appears to be bonded to the nitrogen atom maintaining the trigonal symmetry of the center. The defect is observed by electron paramagnetic resonance in the negative charge state in samples containing a suitable electron donor (e.g., substitutional nitrogen N(0)(S)).

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New ENDOR measurements on the single substitutional nitrogen centre in diamond are reported. The CW-ENDOR mechanism utilizes cross relaxation, and measurements have been made on both 14N and 15N, as well as the first detailed 13C ENDOR study on the isotope at the natural abundance of 1.1%. The change in EPR intensity induced by driving the 13C nuclear transitions was approximately equal to 100% of the EPR intensity of the appropriate 13C hyperfine satellite. The assignment of 13C hyperfine coupling matrices with specific sites is considered, and predictions made about the signs of some of the 13C hyperfine interactions.